Chapter 16 Stable and Radioactive Isotopes Jim Murray 5/7/01 Univ. Washington

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1 Chapter 16 Stable and Radioactive Isotopes Jim Murray 5/7/01 Univ. Washington Each atomic element (defined by its number of protons) comes in different flavors, depending on the number of neutrons. Most elements in the periodic table exist in more than one isotope. Some are stable and some are radioactive. Scientists have tallied more than 3600 isotopes, the majority are radioactive. The Isotopes Project at Lawrence Berkeley National Lab in California has a web site ( that gives detailed information about all the isotopes. Stable and radioactive isotopes are the most useful class of tracers available to geochemists. In almost all cases the distributions of these isotopes have been used to study oceanographic processes controlling the distributions of the elements. Radioactive isotopes are especially useful because they provide a way to put time into geochemical models. The chemical characteristic of an element is determined by the number of protons in its nucleus. Different elements can have different numbers of neutrons and thus atomic weights (the sum of protons plus neutrons). The atomic weight is equal to the sum of protons plus neutrons. The chart of the nuclides (protons versus neutrons) for elements 1 (Hydrogen) through 12 (Magnesium) is shown in Fig The Valley of Stability represents nuclides stable relative to decay. Examples: Atomic Protons Neutrons % Abundance Weight (Atomic Number) Carbon 12C 6P 6N C 6P 7N C 6P 8N Oxygen 16O 8P 8N O 8P 9N O 8P 10N 0.20 Several light elements such as H, C, N, O, and S have more than one stable isotope form, which show variable abundances in natural samples. This variability is caused by isotopic fractionation during chemical reactions. Heavier elements like Pb also have several stable isotopic forms but their distributions are controlled more by their different sources than by fractionation.

2 Fig 16-1

3 16-I. Stable Isotopes All isotopes of a given element have the same electronic structure, thus the bonds they form in any given compound are identical. The differences in mass do give rise to differences in energy levels of vibration. As a result different isotopes of the same element have different vibrational frequencies. These differences lead to small equilibrium fractionations of isotopes between coexisting phases. During a chemical reaction, molecules bearing the light isotope will, in general, react slightly more rapidly than those with the heavy isotope. In principal, equilibrium fractionation can be calculated from fundamental vibrational frequencies. There may also be kinetic fractionations. For example, in a gas the molecules containing the light isotope migrate more rapidly than those with the heavy isotope. This can lead to isotopic fractionation during diffusion. Kinetic fraction can only be measured not calculated. The concentrations of stable isotopes are usually expressed in delta (δ) notation where the ratio of two isotopes in a sample are compared to a standard adopted by the geochemical community and multiplied by 1000 to avoid using fractional values. The use of a standard material results in much greater precision than a direct analysis of absolute ratios for mass spectrometric analyses. The units for δ are usually per mil or parts per thousand (expressed as %o). The delta values are defined as: or δ (in %o) = [(R sample - R standard )/ R standard ] x 1000 R / R std = 1 + δ where R is the isotope ratio with the most abundant isotope in the denominator. When δ = 0%o the isotopic composition of the sample is the same as the standard. 16-I.A. Hydrogen/Deuterium A-1. Rain (to be added) A-2. Air Temperature (to be added)

4 16-I.B. Oxygen Oxygen has three stable isotopes with the following average natural abundances. 16 O % 17 O % 18 O % The standards used for δ 18 O are either Standard Mean Ocean Water (SMOW) or the PDB standard. SMOW was originally a hypothetical seawater sample defined by Craig (1961) which is now provided to the community by the International Atomic Energy Agency (IAEA). The standard used for determination of paleotemperature was originally a Cretaceous belemnite shell from the PeeDee formation in South Carolina, thus PDB. The δ 18 O values of important oxygen containing materials (relative to SMOW) are shown in Fig 16-2 (from Hoefs, 1980). The first mass spectrometric studies of these isotopes in the sea was by Epstein and Mayeda (1953). Most of the water in the atmosphere comes from the ocean and most of the evaporation occurs in the tropics. Net evaporation of water from the oceans produces vapor depleted in 18 O as the lighter isotope, 16 O, evaporates faster than 18 O. Atmospheric circulation transports this water vapor to higher latitudes. As temperature decreases water vapor condenses. Since 18 O is more likely to condense than 16 O the rain is always heavier than the vapor it originates from and the water vapor becomes progressively depleted in 18 O as rain removes water. In this way the δ 18 O of the rain is a function of the water vapor remaining in the atmosphere.

5 This process, in which the isotopic composition of the product varies as a result of the extent of reaction is called a Raleigh Distillation (see Appendix 16-A1 for the derivation). Its effect on the isotope composition of the remaining reactant is given by: R f / R o = f (α-1) Where f is the fraction of remaining reactant, R f is the δ value of the reactant at some f and R o is the δ value when f = 1 (i.e. the initial value)(fig 16-3). In additional to fractional removal, temperature has a large effect. As temperature decreases the fractionation α increases (Fig 16-4). This effect has been taken advantage of to calculate past variations in temperature in Greenland and Antarctic ice core records.

6 B-1. Ice Volume The Raleigh Distillation of water vapor also causes polar ice to be depleted in 18 O relative to seawater. Thus an increase in ice volume causes the ocean to become enriched in 18 O. During periods of maximum glaciation the δ 18 O of seawater increased to +0.90%o (SMOW). If all present-day continental glaciers melted the δ 18 O of seawater would decrease to -0.6%o (SMOW). The calibration relationship for glacial-interglacial sea level change is 0.011%o per meter change in sea level (Fairbanks and Matthews, 1978). The δ 18 O signature of sedimentary carbonates is perhaps the most widely used record of paleoclimate change. The basis for this application is that biogenic calcite forms in isotopic equilibrium with ambient seawater. The δ 18 O composition of planktonic foraminifera is a function of temperature as well. The value is usually reported on the PDB scale as the standard is also a fossil marine carbonate. The δ 18 O record for carefully dated coral reefs from Barbados have provided the first continuous and detailed record of sea level change during the last deglaciation (Fig. 16-5)(Fairbanks, 1989). Sea level was meters below present during the last glacial maximum. The deglacial sea level rise was not monotonic. It was marked by two intervals of rapid rise that occurred approximately 13,070 yr BP and 10,445 yr BP.

7 16-I.C. Carbon Carbon has only two stable isotopes with the following natural abundances: 12 C 98.89% 13 C 1.11% The values of δ 13 C for geologically important materials are shown in Fig 16-6 (Hoefs, 1980). The standard used for carbon isotopes is the same PeeDee Belemnite shell used for oxygen isotopes. Below are some typical δ 13 C values on the PDB scale in %o. Standard (CaCO 3 ; PDB) 0 Atmospheric CO 2-8 Ocean ΣCO 2 +2 (surface) 0 (deep) Plankton CaCO 3 +0 Plankton organic carbon -20 Trees -26 Atmospheric CH4-47 Coal and Oil -26 Photosynthesis produces organic matter which is "depleted" in 13 C relative to the substrate CO 2. Compare the values for trees (-26) versus atmospheric CO 2 (-8) and marine plankton (-20) versus ΣCO 2 (+2)(Fig 16-7). Representative δ 13 C values are shown for living organisms (Fig 16-8) and biochemical constituents (Fig 16-9) (from Degens, 1968). C-1. Primary Production (to be added) C-2. Marine versus Terrestrial (use examples by Sackett, Hedges etc) C-3. Methane Production (see Reeburgh, Martens, Quay for examples)

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9 16-I.D. Nitrogen Nitrogen has two stable isotopes with the following natural abundances. 14 N 15 N Air is the standard used for reporting δ values. Typical values of δ 15 N in some geologically important materials are given in Fig (from Hoefs, 1980). D-1. Food Web Trophic Levels The natural distribution of δ15n has been used to study the vertical processes which transport nitrogen into and out of the euphotic zone. The δ 15 N ratio of particulate organic matter sinking out of the surface ocean is principally a function of the δ 15 N of the source nitrate and isotopic fractionation occurring during partial utilization by phytoplankton. Altabet (1988) reported that for a site near Bermuda the δ 15 N of sinking particles exiting the euphotic zone were about 4%o enriched in δ 15 N relative to suspended particles. This suggestes that only certain components of the suspended pool are selectively transformed into sinking particles. Since δ 15 N is known to increase with each trophic transfer (Fig 16-11) it was inferred that zooplankton contributing to the sinking particle flux fed discriminately on higher trophic level components within the suspended particle pool (e.g. microzooplankton as opposed to phytoplankton). Zooplankton produce fecal pellets that are 1.3%o lower in δ 15 N than their body tissue but 2.2%o higher than their apparent food source (Altabet and Small, 1990). These results show that zooplankton feeding behavior and their digestive chemistry are important in determining the composition of sinking particulate matter in the ocean with respect to the suspended particle source in the euphotic zone. D-2. Denitrification Denitrification is the process by which nitrate is reduced to N 2 and represents the dominant mechanism for removal of fixed nitrogen from the biosphere. Denitrification occurs within the suboxic zones of the world's oceans and is manifest as an increase in N 2 /Ar ratios (Cline, 1973). The main sites of denitrification are in the suboxic ocean regions. These include the eastern tropical north and south Pacific, Arabian Sea and hemipelagic (shelf, slope and rise) sediments throughout the world's oceans. Denitrifying bacteria discriminate against 15 NO 3, producing N 2 gas enriched in 14 N (Cline and Kaplan, 1975; Mariotti et al, 1982; Brandes and Devol, 199x). However, because the background N 2 gas concentration is on the order of 1000 µm N, the additional µm of N 2 from denitrification decreases δ 15 N-N 2 by only %. On the other hand the isotopic composition of the NO 3 remaining is strongly affected. Brandes (1996) results for δ 15 N-N 2 and δ 15 N-NO 3 from the eastern tropical north Pacific are shown in Fig As NO 3 is consumed by denitrification, the δ 15 N-NO 3 goes up while the δ 15 N-N 2 goes down. The values of excess N 2 and δ 15 N-N 2 for the Arabian Sea are shown in Fig 16-13, and for the California shelf and Washington shelf are shown in Fig

10 16-I.E. Sulfur Sulfur has four stable isotopes with the following natural abundances: 32 S 95.02% 33 S 0.75% 34 S 4.21% 36S 0.02% Sulfur isotope compositions are expressed as per mil differences relative to sulfur in an iron meteorite called Canyon Diablo Troilite (CDT) according to: δ 34 S = [( 34 S/ 32 S) sample - ( 34 S/ 32 S) CDT ] / ( 34 S/ 32 S) CDT x 1000 Thode et al (1949) was one of the first to document wide variations in the abundances of sulfur isotopes. The range of δ 34 S in geological materials is shown in Fig (from Hoefs, 1980). It is interesting to note that δ 34 S of seawater sulfate is +20%o. This implies that some process is preferentially removing 32 S from the ocean. This process is probably sulfate reduction which produces 32 S enriched sulfide which can precipitate be removed from the ocean as iron sulfide minerals (pyrite, gregite etc). The δ 34 S of sedimentary sulfides over geological time are highly variable but trends exist which led Canfield (1998) to suggest that there was a sulfide-rich deep ocean in the middle- to late- Proterozoic. E-1. Sulfate reduction Sulfate reducing bacteria produce sulfide depleted in 34 S (enriched in 32 S) by 4 to 46 per mil compared with the starting sulfate. The depletions are variable because this is a kinetic fractionation that occurs during bacterial sulfate reduction. Based on this fractionation we expect sulfide to be depleted in 34 S by large but variable amounts. Field data show much larger fractionation suggesting that the real system even is more complicated. For example, the Black Sea is the classic marine anoxic basin where sulfate reduction is occurring. Enrichment cultures of sulfate-reducing bacteria produce sulfide depleted in 34 S by 26 to 29 per mil, yet water column sulfide is depleted by 62 per mil (Fry et al, 1991). Canfield and Thamdrup (1994) showed that these large fractionations in sulfide could be produced by a scheme where elemental sulfur (S ) is disproportionated to H 2 S and SO 4 2- by sulfurdisproportionating bacteria followed by oxidation of the sulfide to S (Fig 16-16). E-2 Paleo variations in δ 34 S By comparison with sulfides, sulfur is removed to gypsum (CaSO 4. 2H 2 O) with little fractionation of sulfur isotopes. Thus the δ 34 S of gypsum in the geological record should reflect the isotopic composition of ambient seawater sulfate. Variations of δ 34 S in marine sulfate minerals from the Precambrain to the present are shown in Fig The distribution of sulfur isotopes in seawater has clearly changed due to variations in the relative proportions of the oxidized and reduced reservoirs of sulfur (Holland, 1973). Variations in burial and weathering of pyrite are probably the key processes. The present

11 value of δ 34 S-SO 4 is about +20 %o but during the Permian the value was about +10 and at the Cambrian/Precambrian boundary it was greater than +30%o. Garrels and Lerman (1984) and Berner (1987) have modeled these variations (together with variations in δ 13 C) in terms of burial and weathering of 1) organic matter (as CH 2 O), 2) sedimentary carbonates (Ca,MgCO 3 ), 3) sedimentary pyrite (FeS 2 ) and 4) evaporitic gypsum (CaSO 4. H 2 O). The global redox reaction can be written as (Garrels and Perry, 1974): 4FeS CaCO MgCO SiO H 2 O = 8 CaSO 4. 2H 2 O + 2 Fe 2 O CH 2 O + 7 MgSiO 3 The coupled records of δ 13 C and δ 34 S (Fig 16-17) have been used to reconstruct the concentration of atmospheric oxygen over geological history. During the Paleozoic, the ocean became progressively enriched in 13 C and depleted in 34 S because of preferential removal of ocean carbon to organic matter rather than as CaCO 3 and of ocean sulfur to CaSO 4 rather than as FeS 2. There is little doubt that atmospheric O 2 has varied over Phanerozoic time and was higher during the mid-to-late Paleozoic due to increased organic carbon burial however accurate calculations of the atmospheric O 2 concentrations remain difficult (Berner, 1987; 1989).

12 16-II. Radioisotopes 16-II.A. Fundamentals of Radioactive Decay Radioactive decay is a fundamental natural property of many elements in the periodic table. The isotopes of these elements enter the sea from the atmosphere, from rivers, by diffusion from the underlying sediments, and by radioactive decay of other elements within the ocean itself. Radioactive isotopes useful in marine chemistry can be of natural origin (e.g., 14 C, 10 Be, 238 U, 232 Th) or they can be the products of bombs (e.g., 14 C, 90 Sr, 240 Pu) or nuclear reactors (e.g., 239 Pu). Because of their decay, radioactive isotopes are instrumental in the study of many oceanographic and geochemical processes. Decay provides a means of incorporating time and rates into geochemical models. In many instances, radioactive isotopes can also serve as analogues for interpreting the chemistry of non-radioactive elements (e.g., 234 Th, 210 Pb for marine scavenging of reactive elements). In marine chemistry, radioactive isotopes have been used to study the rates of mixing of water and sediments, to calculate the age of water and sediments, and to estimate rates of scavenging and production. 1. The Process of Decay Radioactive decay is the result of the adjustment of the nuclei of atoms from unstable to more stable states. The original radioactive atom is called the parent. The product of the decay is called the daughter. Frequently, a series of successive decay transformation will constitute a decay chain. The use of isotopes to study chemical reactions is facilitated by the fact that the decay process is a function of the stability of the nucleus and is independent of the chemical state. As a result of radioactive decay energy is released as radiation in the form of alpha particles, positive and negative beta particles (positrons and electrons), gamma rays and x-rays. Alpha particles result primarily from the decay of isotopes of high atomic number. These particles consist of two protons and two neutrons and thus are identical to helium nuclei. They are commonly emitted from natural radioactive materials with an energy of three to eight million electron volts (mev). An electron volt is the kinetic energy acquired by an electron falling through a potential difference of 1 volt. It is equivalent to x erg. The resulting daughter product is an element two protons lighter in the periodic table (see Fig 16-1). Negations or electrons (e ) are emitted during decay of isotopes with excess neutrons relative to the stable state. This change involves the transition of one of the neutrons into an electron, proton, and neutrino. The proton stays in the nucleus, increasing the atomic number by one, and the electron and the neutrino are ejected from the nucleus. The ejected electron is referred to as a beta particle. If the nucleus has a neutron-proton ratio lower than the stable forms of the element, two processes compete to return the nucleus to stability. One pathway is for a proton in the nucleus to combine with or capture an electron from one of the extranuclear orbitals (usually from the K level). This process is commonly referred to as electron captive (EC). As a result of this process, a characteristic x-ray of the daughter isotopes is emitted when the vacant energy level produced by the electron capture is filled by an

13 electron from a higher energy level. When the amount of energy available in a nucleus with a low neutron proton ratio is at least 1.02 mev (twice the rest mass of an electron), a second process may compete with electron capture. In this situation a proton may transform into a positron (e + ), a neutron, and an antineutrino. The positron and the antineutrino are emitted, leaving the neutron in the nucleus. The resulting daughter has an atomic number one less than the parent. After any of the abovementioned nuclear transformations, the daughter nucleus may still possess more energy than is normal for the stable nucleus. This excess energy is emitted in the form of electromagnetic energy or gamma ( γ ) radiation. All of these forms of energy that result from the decay process (with the exception of neutrinos) can be readily detected after suitable separation chemistry if necessary. The nature of radiation and its detection is discussed more fully in Overman and Clark (1960), Friedlander and Kennedy (1955), and Kruger (1971). In summary, the radioactive decay is: 1) Independent of chemical or physical state. 2) Independent of temperature and pressure. 3) A property only of the nucleus. 2. Mathematical Formulation of Decay The decay rate of a collection of radioactive isotopes is proportional to the number of atoms present. The proportional constant is called the decay constant and the equation has the form of a typical first order reaction. This can be shown theoretically by assuming radioactive decay to be a random process and applying probability considerations. The incremental change in the number of atoms per incremental change in time is equal to the rate of radioactive decay. dn / N dt =λ (16.1) The negative sign appears since the number of radioactive atoms decreases with time. This equation can be rewritten as: dn = λn (16.2) dt where N = the number of atoms of the radioactive substance present at time t λ = the first order decay constant (time -1 ) The units of λ are reciprocal time. For example, the decay constant for 238 U is 2.22 x 10-1 yr -1. This means that 22 percent of the atoms disintegrates per billion years. The number of parent atoms at any time t can be calculated as follows. Equation 16.2 can be rearranged and integrated over a time interval. N N o dn N = λ dt t 0 (16.3)

14 where N o is the number of parent atoms present at time zero. Integration leads to ln N N o = λt (16.4) or N = N o e λt (16.5) Thus if we start with a fixed number of parent atoms that are not replenished with time, the number of atoms will decrease exponentially with time. The rate of decrease will depend on the magnitude of the decay constant. It is common practice in marine geochemistry to analyze for radioactive isotopes by determining the decay per unit time. This disintegration rate is referred to as the activity and is equivalent to the decay constant times the number of atoms present or: A = N λ (16.6) In many instances it is also more convenient to model oceanographic data in terms of activity. Equation (16.5) can be expressed in terms of activity. or N N o = A A o = e λt (16.7) ln A A o = λt (16.8) or log A λt = A o The unit of absolute activity used as a reference is the Curie which by IUPAC convention (IUPAC, 1951) is defined as x dps (decays per second). The units of activity used in the oceanographic and geochemical literature depend on the magnitude of the decay rate of interest. In addition, the activity is also commonly referenced to a unit of volume or weight such as dpm/kg sed or dpm/10 3 l. The kilogram is normally preferred to liter in oceanographic measurements because it is independent of temperature and pressure. (16.9) 3. Half Life The half life is defined as the time required for half of the atoms initially present to decay. After one half life: Thus N N o = A A o = 1 2 (16.10) 1 ln 2 = λ t 1/2 (16.11)

15 so ln (2) = λ t 1/2 (16.12) = λ t 1/2 (16.13) t 1/ 2 = λ (16.14) 4. Mean Life The mean life is equivalent to the average life of a radioactive atom. Numerically it is the sum of the times of existence of all the atoms initially present divided by the initial number or: 0 τ = 1 N o tdn N o = 1 N o tλn o e λt dt 0 =λ te λt dt 0 = 1 = λ λt +1 λ e λt 0 The mean life, then, corresponds to the time required for the activity to decrease by the factor of e -1. Thus the mean life is greater than the half life by 1/ The difference arises because of the weight given in the averaging calculation to the fraction of atoms that by chance survive for a long time. (16.15) (16.16) (16.17) (16.18) Example 16-1 One gram of 238 U contains 2.53 x nuclei, all of which were formed about 4.5 x 10 9 years ago with the rest of our planet. By coincidence the half life of 238 U is also 4.5 x 10 9 years, which means we presently have on earth only about half of the 238 U initially present. The mystery of radioactive decay is that for billions of years a 238 U nucleus behaves like any other non-radioactive nucleus until suddenly it emits an alpha particle and transforms in 234 Th.

16 5. Parent-Daughter Relationships Example 16-2 An important oceanographic example of secular equilibrium is the decay of 226 Ra with a half life of 1620 years to 222 Rn with a half life of days. The growth of 222 Rn from 226 Ra is shown graphically in Figure The initial growth of 222 Rn is a function of the half life of 222 Rn as can be seen from the general equation for in growth of the daughter (as derived from Equation 16.5): ( A B = ( A A,0 ) 1 e t / t ) 1/ 2,B (16.19) If necessary, the half life of the daughter can be determined from the rate of in growth of the daughter. No information about the half life of the long-lived parent can be obtained from the growth of the short lived daughter. However, there are frequently situations where the activity of a parent is conveniently measured by measuring the equilibrium activity of its daughter. An important example is 228 Ra which emits a weak β and is more conveniently analyzed by measuring the alpha decay of its daughter 228 Th. At secular equilibrium the activities of 228 Ra and 228 Th are equal. Using the equation given above, we can see that after five daughter half lives the activity of the daughter is within 3% of that of the parent. t/t 1/ 2 A B /A A,

17 Example 16-3 For decay chains involving several nuclides, all isotopes in the chain will be in secular equilibrium (A A = A B = A C = A D = etc.) if the parent has a long half life relative to all of the daughters. The total disintegration rate will be either λa A or λa A0 depending on whether the decay of the parent is negligible. The 238 U decay chain is a prime example (Figure 16-19). The half life of the parent 238 U is more than 10 4 greater than the second largest half life in the decay chain ( 234 U: 2.5x10 5 yr). Within a few million years of the formation of the earth, the total activity from this decay chain was equal to 12 λ( 238 U). Now that about one half life of 238U has elapsed, the total radiation from this decay chain is about half what it was during the early days of the earth's history. Example 16-4: 228 Ra- 228 Th 228 Ra with a half life of 6.7 years decays to 228 Th which has a half life of 1.9 years. 228 Ac is an intermediate with a half life of 6.1 hours which we will ignore in this example. The in growth of 228 Th and decay of both isotopes is shown in Figure (not shown here). The equilibrium activity ratio of 228 Th to 228 Ra is 1.39.

18 B. Classification of Isotopes There are three main groups of radionuclides used in marine geochemistry that can be classified according to their modes of formation: 1) Those naturally occurring nuclides that were present during the early stages of the formation of the earth 4.5x10 9 years ago. 2) Radioactive nuclides that are continuously produced through cosmic-ray interaction with atmospheric gases. 3) Man-made nuclides introduced during the past few decades from atmospheric atomic and hydrogen bomb explosions and as wastes from nuclear reactors and reprocessing plants. The half lives of the main parent isotopes in the first group are on the order of billions of years, i.e., long enough for there to still be some present. Of major importance in marine geochemistry are the three long decay chains of 238 U, 235 U, and 232 Th (Figure 16-19). In addition, 40 K and 87 Rb, which decay to stable nuclides, are used frequently in age-dating. A summary of isotopes used in age-dating is given in Table 16-1 (Goldberg and Bruland, 1974). The cosmic ray-produced radionuclides are summarized in Table C and 3 H have been the isotopes most commonly used in oceanographic studies. As analytical techniques have improved, applications have been made of 10 Be, 26 Al, and 32 Si. Other isotopes on this list have potential use, especially 39 Ar. The artificially produced radionuclides that have been detected in the marine environment are listed in Table 16-3 (from Preston, 1974). The nuclides are separated according to those produced from fission reactions (bombs) and neutron activation (reactors). The modes of decay and half lives are also given.

19 Appendix 16-A1: Raleigh Fractionation Any isotope reaction carried out so that the products are isolated from the reactants will exhibit a characteristic trend in isotopic composition called Raleigh Fractionation. For example consider the progressive formation and removal of raindrops from a cloud. The isotopic composition of the residual water vapor in the cloud is a function of the fractionation factor between vapor and water droplets. The isotopic composition of the rain and cloud can be calculated as follows: Let A represent the amount of a species containing the major isotope and B the amount containing the trace isotope. The rate each species reacts is proportional to its amounts; thus and da = k A A db = k B B Since the isotopes react at slightly rates, k A k B. We define the ratio of these two rate constants as k A /k B = α Thus d B /d A = α B/A If we rearrange and integrate from some initial values (A, B ) to the present values (A, B) We obtain db/b = α da/a Integrating or ln B/B = α ln A/A B/B = (A/A ) α Dividing both sides by A/A and rearranging gives B/A = (A/A ) α B /A Since species B is only a trace fraction of the total A + B the fraction of residual material, f, is equal to A/A. Hence B/A = f α B /A Subtracting unity from both sides

20 B/A - B /A = f α B /A The expression for the per mil change in isotopic composition, δ, is given by (1000) x B/A - B /A B /A Thus δ = 1000 (f α-1-1) The classic example of the Raleigh distillation is the fractionation of oxygen isotopes between water vapor in clouds and rain released from the cloud (Dansgaard, 1964) (Fig 16-3). 18 O is enriched by 10 per mil in the rain drops. Hence the 18 O will be depleted at a rate times faster than 16 O ( α = k 18O /k 16O = 1.010). δ = ( 1 - f 0.10 ) The resulting depletion of the 18 O/ 16 O ratio in the residual cloud water is given as a function of the fraction of the original vapor remaining in the cloud ( f ) (Fig A16-1). As f depends on cloud temperature, the relationship can also be given between isotopic composition and cloud temperature. You can see that the initial drops will be rich in 18 O. As rain is removed the cloud is progressively depleted in 18 O. The 18 O in the rain drops decrease also but they are always enriched relative to the cloud vapor. So the fractionating of oxygen isotopes in rain will depend on cloud temperature but it could also be a function of the history of the air mass. In the studies of Greenland and Antarctic ice cores δ 18 O is usually used to indicate temperature. But the interpretation can be complicated when a site receives rain from air masses with different histories (e.g. Charles et al 199x). The δ 18 O in average annual rainfall is a function of mean annual air temperature as shown in Figure 16-4.

21 Appendix 16-A2 - Parent-Daughter Relationships In many problems of interest in oceanography it is useful to compare the activity of one isotope with its parent or daughter. For example, mixing near the ocean floor is studied using the excess of 222 Rn over its parent 226 Ra. In situ scavenging is studied using the depletion of 210 Pb relative to its parent 226 Ra. For the simple case where a radioactive parent (A) decays to a stable daughter (B) (e.g., 210 Po 206 Pb), the rate of formation of the daughter is equal to the rate of decay of the parent at steady state or: dn B dt =λ A N A =λ A N A,0 e λ A t (16.32) If some of the stable daughter is present initially, then in integrated form: N B = (N A,0 ) (1 e λat ) (16.33) For the more complicated case where the daughter is also radioactive, the rate of formation of the daughter is equal to the rate of production from the parent minus the rate of decay of the daughter. dn B dt =λ A N A λ B N B (16.34) Integration of Equation for the case where there are no daughter atoms present at t=0 leads to: N B = λ A (N A,0 ) λ B λ A e λ At e λ Bt ( ) (16.35) In terms of activity:

22 A B = λ B (A A,0 ) λ B λ A e λ A t e λ Bt ( ) (16.36) If some daughter atoms are present initially, we simply add the term A B,0 e -λ Bt to Equation In terms of these equations we can visualize three limiting cases for the relationship between parent and daughter activity. These three conditions are: 1) t 1/2 (A) > t 1/2 (B) or λ A < λ B 2) t 1/2 (A) = t 1/2 (B) or λ A = λ B 3) t 1/2 (A) < t 1/2 (B) or λ A > λ B Regardless of whether the daughter has a longer or shorter half life, an expression can be derived for the time at which the daughter activity reaches a maximum by setting da B /dt equal to zero and solving for t. Thus: t (AB,max) = 3.323(t 1/2,A )(t 1/2,B ) t 1/2,A t 1/ 2,B log t 1/2,A t 1/2,B (16.37) Case I: Half life of parent greater than that of daughter. When the half life of the parent is greater than that of the daughter the term e λ t A with increasing time and becomes negligible in Equations 6.35 and Thus: A B = λ B(A A,0 ) λ B λ A d λ t A ( )= λ B λ B λ A A A (16.38) A A λ λ = = (1 ) 1 λ λ λ B B A A B A B (16.39)

23 With an appropriate amount of time, the activity ratio of daughter to parent reaches a constant value. The activity ratio will range from 0 to 1 depending on the ratio of λ A to λ B. After this ratio is reached, both the parent and daughter activity decrease with the half life of the parent. When this steady-state situation is reached, the daughter is said to be in "equilibrium" with the parent. As a special case, we have the situation where the half life of the parent is much greater than that of the daughter so that the change in the activity of the parent is negligible during the time for radioactive "equilibrium" to be reached. This condition is referred to as "secular equilibrium." The situation where there is appreciable decay of the parent before equilibrium is reached is referred to as "transient equilibrium." Secular equilibrium implies that λ A is completely negligible relative to λ B and the ratio λ /( λ λ ) equals 1, thus: B B A N A N B = λ B λ A and A A A B = After steady state is reached A B = A A, Transient equilibrium occurs when λ A and λ B are sufficiently similar so that λ B can not be neglected and the ratio of λ B /(λ B λ A) is greater than unity. After transient equilibrium is reached, the parent and daughter decay with the half life of the parent. The steady-state activity of the daughter will exceed the activity of the daughter (see Equation 16.39).

24 Case II: Half-life of parent equal to that of daughter This case will only be discussed briefly as its importance in marine geochemistry is small. If we go back to Equation and set λ A = λ B : dn B dt =λ A A A,0 e λ A t λ B N B (16.43) =λ B A A,0 e λ Bt ( N B ) (16.44) Integrating, we obtain N B = A A,0 t e λ B t = A A t (16.45) and A B =λ B A A t (16.46) Case III: Half life of daughter longer than that of parent There are few important examples of the application of this case to marine geochemistry. The time at which the daughter activity has grown to its maximum value is also given by Equation In this case a state of "equilibrium" is never reached and after sufficient time the activity of the daughter is much greater than that of the parent and the total activity is determined by the activity of the daughter alone.

25 References: A. General: Choppin G.R. and J. Rydberg (1980) Nuclear Chemistry: Theory and Applications. Pergamon Press, Oxford, 667. Friedlander G., J.W. Kennedy and J.M. Miller (1964) Nuclear and Radiochemistry, second edition. Wiley, New York, 585pp. Kruger P. (1971) Principles of Activation Analysis. Wiley-Interscience, New York, 522pp. Overman R.T. and Clark H.M. (1960) Radioisotope Techniques. McGraw-Hill, New York, 476pp. B. Raleigh Fractionation Broecker W.S. and V.M. Oversby (1971) Chemical equilibria in the earth. McGraw-Hill, New York, 318pp. Charles et al (199X) Dansgaard, W. (1964) Stable isotopes in precipitation. Tellus, 16, 436. C. Case Studies Altabet M.A. (1988) Variations in nitrogen isotopic composition between sinking and suspended particles: implications for nitrogen cycling and particle transformation in the open ocean. Deep-Sea Res. 35, Altabet M.A. and L. F. Small (1990) Nitrogen isotopic ratios in fecal pellets produced by marine zooplankton. Geochim. Cosmochim. Acta 54, Berner R.A. (1987) Models for carbon and sulfur cycles and atmospheric oxygen: Application to Paleozoic geological history. Amer. J. Sci., 287, Berner R.A. (1989) Biogeochemical cycles of carbon and sulfur and their effect on atmospheric oxygen over Phanerozoic time. Palaoegraphy, Palaeoclimatalogy, Palaeoecology, 3, Canfield D.E. (1998) A new model for Proterozoic ocean chemistry. Nature, 396, Canfield D.E. and B. Thamdrup (1994) The production of 34 S-depleted sulfide during bacterial disproportionation of elemental sulfur. Science, 266,

26 Cline J. and I.R. Kaplan (1975) Isotopic fractionation of dissolved nitrate during denitrification in the eastern tropical north Pacific Mar. Chem. 3, Degens E.T. (1968) Biogeochemistry of stable carbon isotopes. In: (Eqlinton and Murphy, eds.) Organic Geochemistry: Methods and Results. Springer, Berlin, Epstein S. and T. Mayeda (1953) Variation of 18 O content of waters from natrural sources. Geochim. Cosmochim. Acta, 4, 213. Fairbanks R.G. (1989) A 17,000-year glacio-eustatic sea level record: influence of glacial melting rates on the Younger Dryas event and deep-ocean circulation. Nature, 342, Fairbanks R.G. and R.K. Matthews (1978) Quat. Res. 10, Garrels R.A. and E.A. Perry, Jr. (1974) Cycling of carbon, sulfur and oxygen through geologic time. In:( E.D. Goldberg, ed) The Sea, v. 5, Wiley Interscience, New York, p Garrels R.A. and A. Lerman (1984) Coupling of the sedimentary sulfur and carbon cycles - an improved model. Amer. J. Sci., 284, Holland H.D. (1973) Systematics of the isotopic composition of sulfur in the oceans during the Phanerozoic and its implications for atmospheric oxygen. Geochim. Cosmochim. Acta., 37, Thode H.G., J. Macnamara and C.B. Collins (1949) Natural variations in the isotopic content of sulfur and their significnace. Can J. Res. 27B, 361.